CN103936600A - Method for purifying cationic etherifying agent via phosphate ester extraction agent - Google Patents
Method for purifying cationic etherifying agent via phosphate ester extraction agent Download PDFInfo
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- CN103936600A CN103936600A CN201410152746.4A CN201410152746A CN103936600A CN 103936600 A CN103936600 A CN 103936600A CN 201410152746 A CN201410152746 A CN 201410152746A CN 103936600 A CN103936600 A CN 103936600A
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Abstract
The invention discloses a method for purifying a cationic etherifying agent via a phosphate ester extraction agent. According to the method, the crude product of the cationic etherifying agent is extracted and purified by taking a phosphate ester compound as an extraction agent so as to remove epoxy chloropropane and 1,3-dichloro-2-propanol remaining in the cationic etherifying agent product. When the extraction is carried out, the final extraction agent rich in the epoxy chloropropane and the 1,3-dichloro-2-propanol is regenerated, wherein a regeneration environment is maintained as an alkaline environment by adopting an alkaline liquor; the regenerated extraction agent is recycled aiming at the extraction of the crude product of the cationic etherifying agent; and meanwhile, the recycled epoxy chloropropane is cycled into the synthesized cationic etherifying agent to be utilized. Compared with the prior art, the method disclosed by the invention is simple in process, simple and convenient to operate, less in equipment investment, economical and environmentally friendly.
Description
Technical field
The invention belongs to the purification process of fine chemical product, more particularly, be specifically related to a kind of purification by liquid extraction and renovation process of cationic etherifying agent.
Background technology
At present, domestic production high quality treated starch cationic etherifying agent major part used is from external import.But along with the development of the natural product modified chemical product such as starch, as a kind of etherifying agent of excellent property, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CHPTMAC) consumption will constantly increase.Therefore, seek the optimum process that CHPTMAC produces, significant to the market competitiveness of raising China etherifying agent.But in the thick product of cationic etherifying agent that domestic manufacturer produces, epoxy chloropropane (ECH) and the chloro-2-propyl alcohol of 1,3-bis-(DCP) content are high, reach respectively 1622mgkg
-1and 18472mgkg
-1, the easy crystallization of product.The existence of epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-makes it easily and the generation crosslinking reaction such as starch, badly influences the application performance of cationic starch.
Domestic cationic starch manufacturing enterprise mostly adopts stripping process to remove epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-.Stripping process can effectively reduce the content of organic impurity, but be also faced with energy consumption large (the one ton of thick products C HPTMAC that purifies consumes 1.0-1.5 ton water vapor), what existence generation was simultaneously a large amount of contains epoxy chloropropane and the unmanageable problem of the chloro-2-propyl alcohol of 1,3-bis-organic waste water.According to statistics, 1 ton of thick product of every purification, 1～1.5 ton of organic waste water of average generation, essential substance epoxy chloropropane wherein and the chloro-2-propyl alcohol of 1,3-bis-toxicity are larger, and human body is had to carcinogenesis.According to China's integrated wastewater discharge standard, waste water chloride content <0.5mg/L, the low-concentration organic waste water that stripping produces, the concentration of two kinds of impurity is 1～1.5%, far away higher than state sewage emission standard.Because the foreign matter content in waste water is more low more difficult, the organic waste water of therefore processing the generation of cationic etherifying agent vaporizing extract process is more difficult, and cost is very high, and this is also the great technical bottleneck that is restricting Sustainable Development of Enterprises.Therefore,, in order to study more rational post-treating method, in effectively removing organic impurity, reducing is the major issue of current required solution to the pollution of environment.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the method for the purification cationic etherifying agent of a kind of efficient, economy, environmental protection is provided.Reduce production costs, reduce because vaporizing extract process is used the problem of environmental pollution bringing, make whole technique there is good economy and environment benefit.In conjunction with the Application Areas of cationic etherifying agent, the requirement of purifying for extraction process is that the extraction coefficient of slective extraction agent is as far as possible large, and toxicity is little even nontoxic, and extraction agent can be repeatedly used and regenerate easily greatly to reduce production costs.
For reaching above object, select and investigated multiple extraction agent, as toluene, methylene dichloride, ether, chloroform and the effect of extracting of several phosphoric acid ester extraction agent to the thick product of cationic etherifying agent.Analysis show that phosphoric acid ester extraction agent is relatively applicable to the purification by liquid extraction of cationic etherifying agent.For this kind of extractants, determine the processing condition of its extraction, investigate the impact of its technological condition of regeneration on regeneration effect, determine best technological condition of regeneration.
Technical purpose of the present invention is achieved by following technical proposals:
The method of phosphoric acid ester extraction agent purification cationic etherifying agent, carries out purification by liquid extraction using phosphate compounds as extraction agent to the thick product of cationic etherifying agent, with epoxy chloropropane residual in decationize etherifying agent product and the chloro-2-propyl alcohol of 1,3-bis-.In extracting, epoxy chloropropane and 1 will be finally rich in after extraction, the extraction agent of the chloro-2-propyl alcohol of 3-bis-is regenerated, use alkali lye that regenerative environ-ment is maintained to alkaline environment, extraction agent after regeneration recycles for the extraction of the thick product of cationic etherifying agent, and the epoxy chloropropane simultaneously reclaiming is recycled in synthesizing cationic etherifying agent and uses.
Above-mentioned in technique scheme, the volume ratio of the thick product of cationic etherifying agent and extraction agent is 1:(0.4～1).
In technique scheme, extraction temperature is 20-25 degrees Celsius of room temperatures, and extracting pressure is 1 normal atmosphere.
In technique scheme, cationic etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, and in the thick product of cationic etherifying agent, epoxy chloropropane content is up to 1500mgkg
-1above, the chloro-2-propyl alcohol of 1,3-bis-content is up to 15472mgkg
-1above.
In technique scheme, phosphate compounds is selected from tributyl phosphate, three iso-butyl ester of phosphoric acid, tri hexyl phosphate or trioctyl phosphate.
In technique scheme, the regeneration temperature 60-140 of extraction agent DEG C, recovery time 2-6h.
In technique scheme, described alkali lye is the aqueous solution of mineral alkali or organic quaternary ammonium hydroxide, and concentration is mass percent 3.8-8.5wt%, and described mineral alkali is selected from NaOH, KOH or Na
2cO
3; Described organic quaternary ammonium hydroxide is selected from tetrabutylammonium, hydroxide trimethylammonium ethyl ammonium or tetraethyl ammonium hydroxide.
While stating on the implementation extraction scheme, select three stage countercurrent extraction processes, as shown in Figure 1.Utilize pipeline that three extraction cells are connected, and by charging and the discharging direction of selected extraction agent and thick product, to realize the counter-current extraction process of extraction agent and thick product in each extraction cells.After the 3rd the final discharging of extraction cells, in thick product, impurity has met product requirement, and extraction agent enters regeneration unit simultaneously, and after regeneration, extraction agent is back in extraction cells and recycles, and epoxy chloropropane is recycled in synthesizing cationic etherifying agent and uses.
Adopt above-mentioned three stage countercurrent extraction modes, adopt according to actual needs operate continuously, or periodical operation.
Compared with prior art, the invention has the advantages that: 1, technique is simple, easy and simple to handle; 2, facility investment few (being zero input substantially); 3, to have boiling point high for phosphoric acid ester extraction agent, and in water, solubleness is little, the feature of stable in properties; 4, after phosphoric acid ester extractant regeneration, result of use is good, economy, environmental protection.
Brief description of the drawings
Fig. 1 is three stage countercurrent continuous extraction process schematic diagram in technical solution of the present invention, wherein A is one-level extraction cells, B is secondary extraction cells, C is three grades of extraction cells, D is regeneration unit, 1 enters pipeline (light phase feeding pipe) for extraction agent, 2 is thick product introduction pipeline (heavy phase feeding pipe), 3 and 6 is thick product connecting pipeline, 4 and 5 is extraction agent connecting pipeline, and 7 is thick product discharge pipeline (heavy phase discharging pipeline), and 8 is extraction agent discharging pipeline (light phase discharging pipeline), 9 is epoxy chloropropane discharging pipeline, and 10 is extraction agent return line.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment mono-
Taking trioctyl phosphate as extraction agent purification cationic etherifying agent is as example:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epoxy chloropropane content is 1622mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 18472mgkg
-1.Extraction agent is with V
thick product: V
extraction agentthe ratio of=1:0.7, after 1 continuous extraction, in cationic etherifying agent, epoxy chloropropane content is 15mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 32mgkg
-1; After 2 continuous extractions, in cationic etherifying agent, epoxy chloropropane content is 6mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 12mgkg
-1.
2, regeneration
The regeneration condition of trioctyl phosphate: concentration is the 7%NaOH aqueous solution, 120 DEG C of temperature, recovery time 3h, recycle after 6 times, and in the extracted products of regenerating extracting agent, epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-content are still lower than 40mgkg
-1.Illustrate that trioctyl phosphate can be repeatedly used through regenerative process, can effectively save use cost.
Embodiment bis-
Taking three iso-butyl ester of phosphoric acid as extraction agent purification cationic etherifying agent is as example:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epoxy chloropropane content is 1622mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 18472mgkg
-1.Extraction agent is with V
thick product: V
extraction agentthe ratio of=1:0.8, after 1 continuous extraction, in cationic etherifying agent, epoxy chloropropane content is 36mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 70mgkg
-1; After 2 continuous extractions, in cationic etherifying agent, epoxy chloropropane content is 10mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 15mgkg
-1; After 4 continuous extractions, cationic etherifying agent does not detect epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-.
2, regeneration
The regeneration condition of three iso-butyl ester of phosphoric acid: concentration is 6%Na
2cO
3the aqueous solution, 100 DEG C of temperature, recovery time 4h, recycle after 4 times, the extracted products of regenerating extracting agent in epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-content still lower than 50mgkg
-1.Illustrate that three iso-butyl ester of phosphoric acid can be repeatedly used through regenerative process, can effectively save use cost.
Embodiment tri-
Taking tributyl phosphate as extraction agent purification cationic etherifying agent is as example:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, ECH content is 1885mgkg
-1, DCP content is 23265mgkg
-1.Extraction agent is with V
thick product: V
extraction agentthe ratio of=1:1.1, after 1 continuous extraction, in cationic etherifying agent, epoxy chloropropane content is 46mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 82mgkg
-1; After 2 continuous extractions, in cationic etherifying agent, epoxy chloropropane content is 18mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-Content is 25mgkg
-1.
2, regeneration
The regeneration condition of tributyl phosphate: concentration is the 5% tetrabutylammonium aqueous solution, 120 DEG C of temperature, recovery time 6h recycle after 6 times, and in the extracted products of regenerating extracting agent, epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-content are lower than 50mgkg
-1.Illustrate that tributyl phosphate can be repeatedly used through regenerative process, can effectively save use cost.
Embodiment tetra-
Taking tri hexyl phosphate as extraction agent purification cationic etherifying agent is as example:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epoxy chloropropane content is 1895mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 20269mgkg
-1.Extraction agent is with V
thick product: V
extraction agentthe ratio of=1:0.6, after 1 continuous extraction, in cationic etherifying agent, epoxy chloropropane content is 48mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 85mgkg
-1; After 2 continuous extractions, in cationic etherifying agent, epoxy chloropropane content is 15mgkg
-1, the chloro-2-propyl alcohol of 1,3-bis-content is 25mgkg
-1.
2, regeneration
The regeneration condition of tri hexyl phosphate: concentration is the 5% tetraethyl ammonium hydroxide aqueous solution, 100 DEG C of temperature, recovery time 6h recycle after 4 times, and in the extracted products of regenerating extracting agent, epoxy chloropropane and the chloro-2-propyl alcohol of 1,3-bis-content are lower than 50mgkg
-1.Illustrate that tri hexyl phosphate can be repeatedly used through regenerative process, can effectively save use cost.
While stating on the implementation four embodiment schemes, select three stage countercurrent extraction processes, wherein A is one-level extraction cells as shown in Figure 1, B is secondary extraction cells, C is three grades of extraction cells, D is regeneration unit, 1 enters pipeline (light phase feeding pipe) for extraction agent, 2 is thick product introduction pipeline (heavy phase feeding pipe), 3 and 6 is thick product connecting pipeline, 4 and 5 is extraction agent connecting pipeline, 7 is thick product discharge pipeline (heavy phase discharging pipeline), 8 is extraction agent discharging pipeline (light phase discharging pipeline), 9 is epoxy chloropropane discharging pipeline, 10 is extraction agent return line.Utilize pipeline that three extraction cells are connected, and by charging and the discharging direction of selected extraction agent and thick product, to realize the counter-current extraction process of extraction agent and thick product in each extraction cells.After the 3rd the final discharging of extraction cells, in thick product, impurity has met product requirement, and extraction agent enters regeneration unit simultaneously, and after regeneration, extraction agent is back in extraction cells and recycles, and epoxy chloropropane is recycled in synthesizing cationic etherifying agent and uses.
Above the present invention is done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, amendment or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. the method for phosphoric acid ester extraction agent purification cationic etherifying agent, it is characterized in that, using phosphate compounds as extraction agent, the thick product of cationic etherifying agent is carried out to purification by liquid extraction, with epoxy chloropropane and 1 residual in decationize etherifying agent product, the chloro-2-propyl alcohol of 3-bis-, wherein said cationic etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, the volume ratio of the thick product of described cationic etherifying agent and extraction agent is 1:(0.4～1), described phosphate compounds is selected from tributyl phosphate, three iso-butyl ester of phosphoric acid, tri hexyl phosphate or trioctyl phosphate.
2. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 1, it is characterized in that, in extracting, epoxy chloropropane and 1 will be finally rich in after extraction, the extraction agent of the chloro-2-propyl alcohol of 3-bis-is regenerated, use alkali lye that regenerative environ-ment is maintained to alkaline environment, the extraction agent after regeneration recycles for the extraction of the thick product of cationic etherifying agent, and the epoxy chloropropane simultaneously reclaiming is recycled in synthesizing cationic etherifying agent and uses.
3. according to the method for the phosphoric acid ester extraction agent purification cationic etherifying agent described in claim 1 or 2, it is characterized in that, extraction temperature is 20-25 degrees Celsius of room temperatures, and extracting pressure is 1 normal atmosphere.
4. according to the method for the phosphoric acid ester extraction agent purification cationic etherifying agent described in claim 1 or 2, it is characterized in that, in the thick product of cationic etherifying agent, epoxy chloropropane content is up to 1500mgkg
-1above, the chloro-2-propyl alcohol of 1,3-bis-content is up to 15472mgkg
-1above.
5. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 2, is characterized in that, the regeneration temperature 60-140 of described extraction agent DEG C, recovery time 2-6h.
6. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 2, it is characterized in that, described alkali lye is the aqueous solution of mineral alkali or organic quaternary ammonium hydroxide, and concentration is mass percent 3.8-8.5wt%, and described mineral alkali is selected from NaOH, KOH or Na
2cO
3; Described organic quaternary ammonium hydroxide is selected from tetrabutylammonium, hydroxide trimethylammonium ethyl ammonium or tetraethyl ammonium hydroxide.
7. according to the method for the phosphoric acid ester extraction agent purification cationic etherifying agent described in claim 1 or 2, it is characterized in that, in the time implementing extraction scheme, select three stage countercurrent extraction processes, utilize pipeline that three extraction cells are connected, and by charging and the discharging direction of selected extraction agent and thick product, to realize the counter-current extraction process of extraction agent and thick product in each extraction cells, after the 3rd the final discharging of extraction cells, in thick product, impurity has met product requirement.
8. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 2, it is characterized in that, in the time implementing extraction scheme, select three stage countercurrent extraction processes, utilize pipeline that three extraction cells are connected, and by charging and the discharging direction of selected extraction agent and thick product, to realize the counter-current extraction process of extraction agent and thick product in each extraction cells, after the 3rd the final discharging of extraction cells, in thick product, impurity has met product requirement, extraction agent enters regeneration unit simultaneously, after regeneration, extraction agent is back in extraction cells and recycles, epoxy chloropropane is recycled in synthesizing cationic etherifying agent and uses.
9. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 7, is characterized in that, adopts three stage countercurrent extraction modes, adopts according to actual needs operate continuously, or periodical operation.
10. the method for phosphoric acid ester extraction agent purification cationic etherifying agent according to claim 8, is characterized in that, adopts three stage countercurrent extraction modes, adopts according to actual needs operate continuously, or periodical operation.
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Cited By (1)
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